Acceleration of vaporization of chlorine in a battery



P 1952 E. A. SCHUMACHER 2,610,985

ACCELERATION OF VAPORIZATION OF CHLORINE IN A BATTERY Filed Jan. 12, 1949 \NVENTOR ERWIN A. SCHUMACHER ATTORNEY i atenteci Sept. 16, 1952 UNITED: STATES PATENT OFFICE acoettmriou or V POBJZA'H N or QHLOBINE IN A BATTERY Erwin A; Schumacher, Cleveland, Ohio, assignor, by meme-assignments, to Union Garbide'and GarbonCorporation, a corporation oi Ncw York ApPfioationJanuary 12, 1949, Serial no. wiser.

This invention relates to the" activation of a chlorine depolarizedbattery'of primary cells and hasfor an object to expedite the activation of lfillcha battery. Another object is to rapidly vaporize liquefied chlorine making'it available to be taken up by the'batteryi cells, Still another O l'ectis' toprovide heat for ap ri ing chl r ne without, having objectionable reaction" products formed which a e dang s an in ur s to operation of the batt ry;

.It' l 'known to make deferr d ac ion i ary c lsi'in: w icl all f't 'e' el ctroche ical e men othe than the depo a zer e em le in a container or casing; and" to activatethe cellsfor use by introducing the" depolarizer into the container, somecells of this prior art kind areac tivat'edby gaseous chlorine; the chlorine being stored, during the. inactiveperiod of the cell, adjacent to the cell container.

' Chlorine is best stored as liquid sincein this form it has small volume andis" easily transported insteel cylind'ers. However, for activation of the chlorine depolarized battery it is essentialto vaporize the liquid chlorine. Where extremely rapid activation ofthe battery isneeded, heat is necessary within theba-ttery casingto efiectia rapid' change of liquid chlorine into gaseous form. I'f'heat from combustion or some carbonaceous fuel used, the products of combast on re objectionab e; more v such e ;ineme nsi ay be slow, or ifificult' to co tro The heat of reaction obtained the iormation or the chlo idessoi a num e of m talsp e p sure to ch orinehas b en .fou-n l adeq te-to carry on the vacori atlo 'of th hlorin after the-rea tion has started, 7 Acc di to this invention. it h eer o covered that satisfactory speed in activationoi the batte y is obtainedby rin in llquid chlor into: contact with a foil or: filament of a metal having a high heat of reaction with chlorine, as, for example, aluminum, magnesium, tin, or zinc, coated with an adhesive which preferably also reacts with the chlorine to produce heat, such as a rubber cement, on which adhesive is a powdered metal which is reactive with chlorine. The powdered metal on the adhesive should be finely divided but need not have a high heat of reaction: copper is satisfactory, for instance.

A suitable reaction mass comprises a thin foundation metal of aluminum foil or wire coated with a reactive rubber adhesive and dusted while moist with antimony or copper powder. In place of the aluminum, zinc or magnesium can be used in thin sheets or strips or wire secured. A reactivebonding medium such as turpentine having .rsoiaams. (cit esss) 2. incorporated therein small quantities of onsaturated oils, for example, linseed oil may be used as the adhesive. The reaction material preferably is placed adjacent the outlet of the li uid chl r o ge y i d s, t P t i it may also be pl ced n er he" ba 'e yto ssi t i dDOriZing the i u d i o s un e t battery. V

The single gur f th drawing illust ates a hlo ine acti a d a ery ha in im ro ed chlorine" reactive material on" the "bottom 913" the casing belOW the battery.

The battery Iii-illust ated s" of the chlorine d o a d e s wn theii i rapll c ti of Zimm'erman'et al., Serial o; 53.174, f led Octob r 1948, n Pa en l72;1 Primary Gell andBattery'andMethod qfMalgiijig Same. This a e y ism m d on su pmt H elicj scasinsilii quid ch orinefrorn a supply cy er or th app riate source Q s pl ent the casin t h let p p 14 m nity a v l p pe wlthiits c n rol valve l "leadsto ava um u om'o de at a ine t a- 'w m e cas n uri g ore-a at n li e may b rawn befor a lowi the ctivat g chlorineto er: 0. admission o t e c a g ch o liqu d to it a s y gravity to the bottom or, the a ne' icr t tacts ercac n materi l 1' iii fo l r lam ry o m' a ed unde batt ry for produ i the q i i h atto vapor;- ize'thech'lorine rapidly,

The ea i n material in lu f d ti metal in i91 orfi amen arv rm whi h i r active wit rme toevo e the heat needed for va ri in t chlorin for c iva i n of t battery. 'Uponthefoundation a chlorine reactive adhesive with chlorine reactive metal powdered p t les an r to t e urf c of theiofl r filament b the h sive: h meta ch ori e; reac ion productsar mra'blv dep sit an inne s riaci 10f ithe en ms we e where they are harmless" to satisfactory operation of" the battery. Further details of the reactive material follow,

Specifically, one part by weight of aluminum filaments is coated with 0.1 to 0.2 part rubber deposited from a benzene solution and then dusted while moist with two parts of finely divided antimony powder. With the proportions given, the adhesive coating is not substantially thicker than the filament and is usually as thin or thinner. A handbook gives the heat of formation of ferric chloride as 96.30 kilogram calories per gram formula weight, and the heat of reaction of chlorine with aluminum, zinc, tin, and :mag-

"would the foundation alone.

2,610,985 f, xi) 1.

nesium as being greater than this amount. The Metals Handbook defines foil as being not more than about .005 inch thick. Part of the foil so treated and coated is located near the outlet from the liquid chlorine containers and part is arranged longitudinally between the battery and its casing. I

Among the advantages of this invention may be mentioned that the materials mentioned are stable under storage conditions, retain their sensitivity to chlorine, and have no deleterious eflect on the battery. The conversion products do not affect the battery adversely.

What is claimed is:

1. A method of vaporizing liquid chlorine which comprises bringing liquid chlorine into contact with a metal chlorine reactive body, said body comprising a foundation metal notmore than .005 of an inch thick, said foundation metal being coated with an adhesive which is reactive .with chlorine, and finely divided chlorine-reactive metal bound to said foundation by said adhesive, and vaporizing the liquid chlorine rapidly by the heat of reaction of said liquid chlorine with said metal body.

-2. A method according to claim 1 in which the foundation metal is filamentary aluminum.

' 3. A method according to claim 1 in which aid adhesive is a rubber cement.

' 4; A method according to claim 1 in which the foundation metal is selected from the class containing magnesium and zinc.

5. A method according to claim 1 in which the foundation metal is aluminum.

6. A-method according to claim 1 in which the .foundation metal is tin.

7. YA method according to claim 1 in which the foundation metalis iron.

8. An article of manufacture for rapidly vaporizing liquid chlorine comprising a foundation metal having a high heat of reaction with liquid chlorine and in at least one of foil and filalmentary form to provide large exposed surfaces, [an adhesive which is not substantially thicker than the foundation and is reactive with chlorine, coating at least some of said surfaces, and a finely powdered chlorine reactive metal dusted on said adhesive and secured to said foundation metal "surfaces by said adhesive, said adhesive being less in weight than the attached powder, whereby liquid chlorine more rapidly on contact than 1, 9. An article of manufacture according to .claim 8 in' which said foundation metal is from the class consisting of magnesium and zinc.

' 10. An article of manufacture according to claim 8 in which said foundation metal is aluminum.

' 11. An article of manufacture according to claim 8 is which said foundation metal is tin.

' 12. An article of manufacture according to claim. 8 in which said foundation metal is iron.

13. In a chlorine depolarized battery having an enclosing casing surrounding said battery, and means for the supply of liquid chlorine inside of said casing for activating the battery, the combination therewith of the improvement for rapidly vaporizing liquid chlorine within the casing and without the formation of objectionable comvaporizing liquid chlorine, comprising a chlorine reactive finely divided metal powder dusted on a chlorine reactive adhesive coating on a foundation, said adhesive coating being thin and a minor fraction of the weight of the attached powder, said foundation being in at least one of foil and filamentary form not more than about .005 inch thick and having a heat of reaction with chlorine of at least as much as 96.36 kilogram calories per gram formula weight, whereby said combination reacts more quickly than does'the foundation alone to vaporize liquid chlorine. 15. An article of manufacture for. rapidly vaporizin liquid chlorine, comprising a. foundation, one part by weight of aluminum filament coated with 0.1 to 0.2 part by weight of rubber adhesive, and the rubber adhesive coated with two parts by weight of finely divided antimony powder. ERWIN A. SCHUMACHEB..

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 629,426 Coleman July 25, 1899 1,717,140 Brandenberger June 11,1929 2,005,360 Boggs June 18, 1935 2,323,169 Wagenhals June 29, 1943 OTHER REFERENCES A Course in General Chemistry, by McPherson and Henderson, third ed., page 589. Ginn-lz Co., N. Y., publishers. I I J. W. Mellors ModernInorganic Chemistry, single volume ed., January 1935, page 460. Long- 'mans, Green & Co., N. Y., publishers.

J. W. Mellors Inorganic and Theoretical Chemistry, 1922 ed., vol. 2, page 92. Longmans, Green & Co., N. Y., publishers. I

Hackhs Chemical Dictionaryjf third ed., 1944, page 529, by J. Grant. The Blakiston Co., Philadelphia, publishers. 

1. A METHOD OF VAPORIZING LIQUID CHLORINE WHICH COMPRISES BRINGING LIQUID CHLORINE INTO CONTACT WITH A METAL CHLORINE REACTIVE BODY, SAID BODY COMPRISING A FOUNDATION METAL NOT MORE THAN .005 OF AN INCH THICK, SAID FOUNDATION METAL BEING COATED WITH AN ADHESIVE WHICH IS REACTIVE WITH CHLORINE, AND FINELY DIVIDED CHLROINE-REACTIVE METAL BOUND TO SAID FOUNDATION BY SAID ADHESIVE, AND VAPORIZING THE LIQUID CHLORINE RAPIDLY BY THE HEAT OF REACTION OF SAID LIQUID CHLORINE WITH SAID METAL BODY. 